Acrylates and actinic radiation-curable compositions containing them

ABSTRACT

New imido(meth) acrylates of general formula (1), wherein R 1 , R 2  and R 3  may be the same or different and each represents H or CH 3 ; R 4  to R 7  may be the same or different and each represents H or C m H 2m+1  (in which m is 1 to 6); and n represents 1 to 4, and radiation-curable compositions prepared from them, easily cured by the irradiation with radiations, particularly ultraviolet rays, to form cured compositions excellent in weather resistance, abrasion resistance and adhesion to a base, and free from the problem of odor.

This application is the national phase of international applicationPCT/JP98/02737 filed Jun. 19, 1998 which designated the U.S.

TECHNICAL FIELD

The present invention relates to new acrylates and compositions whichcomprise the acrylates and are curable by irradiation with radiationssuch as electron rays and ultraviolet rays, namely, radiation-curablecompositions. Since coating films or molded articles can be derived fromthe compositions and are excellent in weather resistance and abrasionresistance, the compositions of the present invention can be utilized ascoating agents, adhesives and molding materials. That is, the presentinvention belongs to paints, adhesives and plastic molding technique.

BACKGROUND ART

Due to their rapid curability, for radiation-curable compositions,energy and time required for drying can be much reduced as compared withthe conventional solvent type resin compositions, and, in addition,drying apparatuses are not needed. Thus, saving of spaces can beattained. Furthermore, the compositions require only a small amount ofsolvents or require no solvents. For these reasons, they are used in ayearly increased amount as materials safe for earth environment.

Moreover, recently, the radiation-curable compositions expand in theiruse to various fields, but performances required in these fieldssometimes cannot be attained by only the combination of oligomers ormonomers conventionally used as starting materials.

On the other hand, molded articles made from polymethyl methacrylateresins, polycarbonate resins, etc. have various advantages such as lightweight and excellent shock resistance and, easy processing, and are usedin many fields. However, since these plastic molded articles areinsufficient in abrasion resistance of the surface, their surface is aptto be damaged and improvement in abrasion resistance is demanded.Furthermore, these molded articles are sometimes used outdoors such asautomobile parts, and are also strongly demanded to have weatherresistance.

In order to improve abrasion resistance, methods of coating the surfaceof these plastic molded articles with ultraviolet-curable compositionshave been investigated. However, these compositions are sometimesinsufficient in abrasion resistance and adhesiveness to plastics, andeven if these performances are satisfied to some extent, in many cases,there are problems in weather resistance.

That is, in the case of ultraviolet-curable compositions mainly composedof acrylates, which are in most cases used as radiation-curablecompositions, photopolymerization initiators that generate activeradicals by the irradiation with ultraviolet rays must be added to thecompositions for curing them with ultraviolet rays. However, thephotopolymerization initiators remain in cured products of thecompositions and deteriorate weather resistance of the cured products tocause coloration or discoloration, peeling of coat and cracking.Therefore, the ultraviolet-curable compositions are unsatisfactory forthe use requiring weather resistance. Further, decomposition products ofphotopolymerization initiators in the cured products sometimes give odorto the cured products.

Furthermore, it has been attempted to improve weather resistance of thecompositions by adding weather resistance improvers such as ultravioletabsorbers, light stabilizers and antioxidants, but the effect is stillinsufficient and, besides, there are problems that the weatherresistance improvers hinder the curing reaction to cause deteriorationin ultraviolet-curability of the compositions and result in reduction ofproductivity.

Recently, it has been found that N-substituted maleimide compounds havea function as photopolymerization initiators, and it has been reportedthat vinyl ether or an acrylate is polymerized by ultraviolet rayswithout using photopolymerization initiators [Sonny Jonsson et al,Radotech 95 Europe, Previous Lecture Manuscripts “Academic Day”, page34].

This function of N-substituted maleimide compounds to initiatephotopolymerization is excellent, being different from conventionalphotopolymerization initiators, but since these maleimide compounds aresolid and high in melting point, they are difficult to handle, and,furthermore, they must be dissolved in acrylates in order to use them inthe form of liquid. However, maleimide compounds are sometimes low insolubility in acrylates, and, in this case, if the amount of maleimidecompounds is increased, they are precipitated. Due to these problems,only curable compositions of limited formulations can be produced, andwhen formulations of compositions are changed depending on theproperties demanded in various uses, the compositions do not satisfy thedesired properties.

In addition, these maleimide compounds are low-molecular weightcompounds, and when they are added to curable compositions as acomponent having a function as photopolymerization initiators, if theyremain without being bonded to the cured products, characteristics ofthe cured products are deteriorated.

Furthermore, these maleimide compounds are generally produced byaddition reaction of maleic anhydride with amines and the subsequentdehydration reaction, but this method produces them in low yields owingto side reaction of unsaturated group of the starting maleic anhydride.A method of production with protecting the unsaturated group wasproposed (JP-A-2-268155), but a step of deprotection reaction is addedand the production is not simple.

Based on the above facts, the inventors have conducted an intensiveresearch in an attempt to find a curable composition which is easy inpreparation of its starting materials, is easily curable by irradiationwith radiations, especially ultraviolet rays, provides cured productsexcellent in weather resistance and abrasion resistance, has no problemof odor, and is excellent in adhesion to substrate.

DISCLOSURE OF INVENTION

As a result of various investigations conducted by the inventors, it hasbeen found that a novel N-substituted maleimide compound, namely, imido(meth)acrylate, solves the above problems. Thus, the present inventionhas been accomplished.

That is, the present invention relates to an imido acrylate representedby the following formula (1).

[wherein R₁, R₂ and R₃ each represents H or CH₃, and R₁, R₂ and R₃ inone molecule may be the same or different, R₄-R₇ each represents H orC_(m)H_(2m+1) (m=1-6), and R₄-R₇ in one molecule may be the same ordifferent, and n=1-4].

Especially, the present invention relates to an imido (meth)acrylatewith R₃-R₇ in the above formula being H, which is represented by thefollowing formula (2).

[wherein R₈ and R₉ each represents H or CH₃ and R₈ and R₉ in onemolecule may be the same or different, and s=1-4].

Moreover, the present invention relates to a polymer having the aboveimido acrylate or the above imido acrylate and other compound having anethylenically unsaturated bond as constitutive monomer units.

In addition, the present invention relates to a radiation-curablecomposition having the above imido acrylate or polymer as an effectivecomponent.

The present invention will be explained in detail below.

In this specification, for assurance of accuracy, acrylate andmethacrylate, acrylic acid and methacrylic acid, and acryloyl group andmethacryloyl group are called (meth)acrylate, (meth)acrylic acid, and(meth)acryloyl group, respectively.

Imido (meth)Acrylate

The imido (meth)acrylates of the present invention are compoundsrepresented by the above formula (1).

When m exceeds 6 in R₄-R₇, curability of the compositions isdeteriorated, and strength of the cured products is also reduced. When nexceeds 4, concentration of imido site in the molecule decreases tocause deterioration of curability. Thus, they are not suitable forobtaining the desired radiation-curable compositions of the presentinvention.

Among the above imido (meth)acrylates, preferred are those representedby the formula (2) which correspond to the compounds represented by theformula (1) where R₃-R₇ are H because the resulting compositions areexcellent in curability and the cured products are excellent instrength.

The imido (meth)acrylates of the present invention are easily cured withradiations, and even when they are cured with ultraviolet rays,photopolymerization initiators are not needed in most cases, and even inthe case of needing the photopolymerization initiators, they are curedat practically sufficient curing speed with use of a small amount of theinitiators, and the cured products have practically sufficientproperties and are excellent in weather resistance.

The imido (meth)acrylates of the present invention can be producedthrough one step, and can be easily obtained by dehydration condensationreaction of an N-hydroxyalkyltetrahydrophthalimide derivative with(meth)acrylic acid.

In more detail, there may be mentioned a method which comprisesdissolving an N-hydroxyalkyltetrahydrophthalimide derivative,(meth)acrylic acid and an acid catalyst in an organic solvent such astoluene, followed by stirring with heating.

The acid catalysts include sulfuric acid, p-toluenesulfonic acid, etc.Amount of the acid catalyst can be optionally set depending on thestarting materials used, but is preferably 0.1-5% by weight in thereaction mixture. Reaction temperature can also be optionally setdepending on the starting materials used, but is preferably 60-150° C.This reaction is a dehydration reaction, and water produced in thereaction is preferably removed from the reaction system. Thus, thereaction temperature is more preferably the boiling point or higher ofthe solvent used. In this case, in order to inhibit the polymerizationof the resulting imido (meth)acrylate, it is preferred to add apolymerization inhibitor such as hydroquinone monomethyl ether.

Furthermore, the N-hydroxyalkyltetrahydrophthalimide used as a startingmaterial in this production method can be prepared through one step bythe addition reaction of a 3,4,5,6-tetrahydrophthalic anhydridederivative with an amino alcohol and the subsequent dehydration reactionwithout protection of the unsaturated bond, and the reactionquantitatively proceeds. As an example of the method, mention may bemade of a method which comprises dissolving a 3,4,5,6-tetrahydrophthalicanhydride derivative and an amino alcohol in an organic solvent such astoluene, followed by stirring with heating. The reaction proceedswithout addition of a particular catalyst, but, if necessary, sulfuricacid, p-toluenesulfonic acid, etc. can be added. Reaction temperaturecan be optionally set depending on the starting materials used, but ispreferably 60-150° C. This reaction is a dehydration reaction, and waterproduced in the reaction is preferably removed from the reaction system.Thus, the reaction temperature is more preferably the boiling point orhigher of the solvent used.

Since the imido (meth)acrylate of the present invention is a compoundhaving a cyclohexyl ring and a (meth)acryloyl group, it is alsoexcellent in solubility in (meth)acrylates, and cured products have aproper hydrophobic property due to the cyclohexyl group resulting fromthe starting imido (meth)acrylate and, hence, are excellent in weatherresistance, especially weather resistance under high humidityconditions. Furthermore, since the imido group unit of the imido(meth)acrylate is of high polarity, the cured film is excellent inadhesion to various synthetic resin molded articles and the curedproducts are excellent in abrasion resistance and weather resistance.

The imido (meth)acrylates can also be prepared by the methods disclosedin the following literatures and patents.

Kiyoshi Kato et al, “Journal of Synthetic Organic ChemistryAssociation”, 30 (10), 897, (1972).

Javier de Abajo et al, “Polymer”, vol.33 (5), (1992).

JP-A-56-53119

JP-A-1-242569

Polymers Having Imido (meth)Acrylates as Constitutive Monomer Units

The imido (meth)acrylates of the present invention can be made intocurable polymers (hereinafter referred to as “imido polymers”) byhomopolymerization or copolymerization with compounds having anethylenically unsaturated double bond, and the polymers can also be usedas starting materials for the radiation-curable compositions.

The imido polymers have the same maleimido groups as of the above imido(meth)acrylates. Therefore, they are easily cured with radiation likethe imido (meth)acrylates, and even when they are cured with ultravioletrays, photopolymerization initiators are not needed in most cases, andeven in the case of needing the photopolymerization initiators, they arecured at practically sufficient curing speed with use of a small amountof the initiators, and the cured products have practically sufficientproperties and are excellent in weather resistance.

As the compounds having an ethylenically unsaturated double bond andcopolymerizable with the imido (meth)acrylates, mention may be made of,for example, aromatic compounds having an ethylenically unsaturateddouble bond, such as styrene and α-methylstyrene, unsaturated carboxylicacids such as (meth)acrylic acid, crotonic acid and cinnamic acid,dimers or higher oligomers which are Michael addition reaction productsof unsaturated carboxylic acids, (meth)acrylonitrile, vinyl acetate, and(meth)acrylates. Specific examples of the (meth)acrylates are alkyl(meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate,butyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl(meth)acrylate; alicyclic alkyl (meth)acrylates such as cyclohexyl(meth)acrylate; substituted aryl (meth)acrylates such as benzyl(meth)acrylate; alkoxy (meth)acrylates such as 2-methoxyethyl(meth)acrylate and 2-ethoxyethyl (meth)acrylate; isobornyl(meth)acrylate; hydroxyalkyl (meth)acrylates such as hydroxyethyl(meth)acrylate and hydroxypropyl (meth)acrylate; and carboxylgroup-containing (meth)acrylates such as ω-carboxypolycaprolactonemono(meth)acrylate, phthalic acid monohydroxyethyl (meth)acrylate andsuccinic acid monohydroxyethyl (meth)acrylate.

Number-average molecular weight of the imido polymers is preferably500-500,000, more preferably 1,000-100,000, especially preferably1,000-50,000. The number-average molecular weight and weight-averagemolecular weight in the present invention are those which are obtainedby calculating by polystyrene standard from the molecular weightsmeasured by gel permeation chromatography (hereinafter referred to as“GPC”) using tetrahydrofuran as a solvent.

More preferred imido polymers are homopolymers of the imido(meth)acrylate represented by the formula (2) or copolymers of the imido(meth)acrylate with an alkyl (meth)acrylate which have alkyl groupshaving 1-8 carbon atoms or styrene, which have a number-averagemolecular weight of 1,000-100,000, preferably 1,000-50,000.

The constitutional proportion of the monomers in the copolymer is imido(meth)acrylate: alkyl (meth)acrylate=1-9:9-1 in molar ratio in the caseof the alkyl (meth)acrylate which have alkyl groups having 1-8 carbonatoms, and imido (meth)acrylate:styrene=2-5:8-5 in molar ratio in thecase of styrene.

The imido polymers can be produced by various processes and bypolymerizing the starting monomers in accordance with conventionalpolymerization processes such as solution polymerization, emulsionpolymerization and suspension polymerization. Among them, solutionpolymerization is preferred because no emulsifiers are needed and theresulting polymers are excellent in weather resistance.

A specific process of the solution polymerization comprises dissolvingthe starting monomer in an organic solvent and adding a thermalpolymerization initiator thereto, followed by stirring with heating. Inthis case, if necessary, a chain transfer agent may be used forcontrolling the molecular weight of the polymers.

The organic solvents include benzene, toluene, ethyl acetate, methanol,dimethylformamide, etc.

The thermal polymerization initiators include peroxides, azo compoundsand redox initiators which generate radical species by heat. Examples ofthe peroxides are benzoyl peroxide, lauroyl peroxide, cumenehydroperoxide, t-butyl hydroperoxide and dicumyl peroxide. Examples ofthe azo compounds are azobisisobutyronitrile andazobis-2,4-dimethylvaleronitrile. Examples of the redox initiators arehydrogen peroxide-iron (II) salt, peroxodisulfate-sodium hydrogensulfiteand cumene hydroperoxide-iron (II) salt. Amount of the thermalpolymerization initiators can be optionally set depending on thestarting monomers used and molecular weight of the desired polymers, andis preferably 0.01-5% by weight in the reaction mixture. The chaintransfer agents include dodecyl mercaptan, disulfide xanthate,diazothioether, 2-propanol, etc.

Reaction temperature can be set depending on the starting monomers used,the thermal polymerization initiators used and molecular weight of thedesired polymers, and is preferably 50-150° C.

Radiation-curable Compositions:

The imido (meth)acrylates and imido polymers of the present inventionhave curability, but in order to obtain excellent radiation-curablecompositions using them, it is preferred to use the following(meth)acrylates (hereinafter referred to as merely “(meth)acrylates”) incombination with them.

Contents of the imido (meth)acrylate and the imido polymer in theradiation-curable composition in the case of using the (meth)acrylate incombination are preferably 5-95% by weight, more preferably 5-50% byweight. If the content of the imido (meth)acrylate or the imido polymeris less than 5% by weight, curability is inferior or strength of thecured products is insufficient, and if it is more than 95% by weight,hardness, tensile strength and abrasion resistance of the cured productsare insufficient.

(Meth)Acrylates:

The (meth)acrylates used together with the imido (meth)acrylates or theimido polymers in the present invention may be any of those which areclassified into monomers and oligomers.

The oligomers include urethane (meth)acrylate, polyester (meth)acrylate,epoxy (meth)acrylate, etc.

The monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl(meth)acrylate and 2-hydroxypropyl (meth)acrylate; acrylates of alkyleneoxide adducts of phenol such as phenoxyethyl (meth)acrylate, andhalogen-aromatic nucleus substitution products thereof; mono- or di(meth)acrylates of glycol such as mono- or di (meth)acrylate of ethyleneglycol, mono(meth)acrylate of methoxyethylene glycol, mono- or di(meth)acrylates of tetraethylene glycol and mono- or di(meth)acrylatesof tripropylene glycol; di- or tri(meth)acrylates of alkylene oxideadducts of isocyanuric acid; and (meth)acrylates of polyols such astrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate,pentaerythritol tetra(meth)acrylate and dipentaerythritolhexa(meth)acrylate and (meth)acrylates of alkylene oxide adducts ofthese polyols. Here, the alkylene oxide includes, for example, ethyleneoxide and propylene oxide.

The urethane (meth)acrylate oligomers include, for example, reactionproducts obtained by reacting hydroxyl group-containing (meth)acrylateswith reaction products of polyols and organic polyisocyanates. Thepolyols here include low-molecular weight polyols, polyethylene glycols,polyester polyols, etc. As the low-molecular weight polyols, mention maybe made of ethylene glycol, propylene glycol, cyclohexanedimethanol,3-methyl-1,5-pentanediol, etc. As the polyether polyols, mention may bemade of polyethylene glycol, polypropylene glycol, etc. As the polyesterpolyols, mention may be made of reaction products of these low-molecularweight polyols or/and polyether polyols with acid components, e.g.,dibasic acids such as adipic acid, succinic acid, phthalic acid,hexahydrophthalic acid and terephthalic acid or anhydrides thereof. Asthe organic polyisocyanates, mention may be made of tolylenediisocyanate, 4,4′-diphenylmethane diisocyanate,4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate,isophorone diisocyanate, etc. As the hydroxyl group-containing(meth)acrylates, mention may be made of hydroxyalkyl (meth)acrylatessuch as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl(meth)acrylate.

The polyester (meth)acrylate oligomers include dehydration condensatesof polyester polyols with (meth)acrylic acid. As the polyester polyols,mention may be made of reaction products of the low-molecular weightpolyols such as ethylene glycol, polyethylene glycol,cyclohexanedimethanol, 3-methyl-1,5-pentanediol, propylene glycol,polypropylene glycol, 1,6-hexanediol and trimethylolpropane and polyolssuch as alkylene oxide adducts thereof with acid components, e.g.,dibasic acids such as adipic acid, succinic acid, phthalic acid,hexahydrophthalic acid and terephthalic acid or anhydrides thereof.

The epoxy acrylates are those obtained by addition reaction of epoxyresins with (meth)acrylic acid, and include (meth)acrylate of bisphenolA epoxy resin, (meth)acrylate of phenol or cresol novolak epoxy resin,(meth)acrylic acid adducts of diglycidyl ether of polyether, etc.

Among these (meth)acrylates, those which have two or more (meth)acryloylgroups in one molecule are preferred because the resulting curedproducts are excellent in hardness and abrasion resistance. Moreover,use of aliphatic or alicyclic compounds as the (meth)acrylates ispreferred because they are superior to compounds having aromatic ring inweather resistance and curability.

Photopolymerization Initiators:

The compositions containing the imido (meth)acrylate or imido polymer ofthe present invention are cured by irradiation with radiations, and aresurely cured even with ultraviolet rays without usingphotopolymerization initiators, but for further improvement ofcurability, photopolymerization initiators can be added as far asweather resistance is not damaged.

Examples of the photopolymerization initiators are benzoins such asbenzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropylether, and their alkyl ethers; acetophenones such as acetophenone,2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone,1,1-dichloroacetophenone, 1-hydroxyacetophenone,1-hydroxycyclohexylphenyl ketone, and2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one;anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone,2-tert-butylanthraquinone, 1-chloroanthraquinone and2-amylanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone,2,4-diethylthioxanthone, 2-chlorothioxanthone and2,4-diisopropylthioxanthone; ketals such as acetophenonedimethylketaland benzildimethylketal; benzophenones such as benzophenone; andxanthones.

These photopolymerization initiators can be used each alone or incombination with photopolymerization initiation accelerators such as ofbenzoic acid type and amine type.

Amount of these photopolymerization initiators is preferably 5 parts byweight or less, more preferably 2 parts by weight or less based on 100parts by weight of the composition.

Weather Resistance Improvers:

At least one weather resistance improver selected from ultravioletabsorbers, light stabilizers and antioxidants can be added to thecompositions containing the imido (meth)acrylate of the presentinvention and the compositions containing the imido polymer for thepurpose of further improvement of weather resistance.

Examples of the ultraviolet absorbers are benzotriazole ultravioletabsorbers such as 2-(5-methyl-2-hydroxyphenyl)benzotriazole and2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole.

The light stabilizers include hindered amine and benzoate lightstabilizers. Examples of the hindered amine light stabilizers arebis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate andbis(1,2,2,6,6-pentamethyl-4-piperidyl)2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate. Examples of thebenzoate light stabilizers are2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxy benzoate.

Examples of the antioxidants are hindered phenol antioxidants such astriethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate]and 1,6-hexanediol-bis[3,5-di-t-butyl-4-hydroxyphenyl]propionate].

Preferred amount of the weather resistance improvers is 0.01-5 parts byweight based on 100 parts by weight of the composition. If the amount isless than 0.01 part by weight, the effect of adding the weatherresistance improver is not obtained, and if it exceeds 5 parts byweight, sometimes curability of the composition lowers or abrasionresistance of the cured products of the composition lowers.

Method of Use:

The composition of the present invention can be used for various usessuch as paints and other coating agents, printing inks, adhesives,fillers, and molding materials. Especially, since the imido group siteof the constitutive imido (meth)acrylate is high in polarity, thecomposition is excellent in adhesion to various plastics and furthermorein abrasion resistance and weather resistance, and thus the compositioncan be used more preferably for hard coats of plastics and moldingmaterials because of the excellent abrasion resistance and weatherresistance.

As for the method of use of the composition according to the presentinvention, there may be employed, for example, a general method whichcomprises coating the composition on a substrate by conventional coatingmethod, followed by irradiating with radiations such as ultraviolet raysand electron rays to cure the coat in the case of the uses as coatingagents, printing inks and adhesives, and a general method whichcomprises pouring the composition into a given frame, followed byirradiating with radiations to cure the composition in the case of usesas fillers and molding materials. As the irradiation method ofradiations, there may be also employed general method known as a methodfor curing of radiation-curable compositions.

The substrates usable for application of coating materials, printinginks and adhesives can be various substrates such as papers, woods,metals and plastics, but the composition of the present invention isespecially preferably applicable to plastics substrates as mentionedabove.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be explained in more detail by the followingexamples, wherein “%” means % by weight and “part” means part by weight.

In Examples 1-15, refractive index was measured using Abberefractometer, and specific gravity was measured in accordance withJISK-6835. The refractive index and the specific gravity were values at25° C. ¹H-NMR and ¹³C-NMR were measured using Model JNM-EX270manufactured by Nihon Denshi Co., Ltd., and IR was measured using FT-IRof Model MAGNA750II manufactured by Nikorey Co., Ltd.

EXAMPLE 1

152 Grams (1.0 mol) of 3,4,5,6-tetrahydrophthalic anhydride and 200 g oftoluene were charged in a flask equipped with a stirrer, a condensertube and a water separator (Dean Stark Trap) and heated to 50° C. todissolve the acid anhydride in toluene. Then, 61.1 g (1.0 mol) of2-aminoethanol was added thereto dropwise over a period of 10 minutes,and thereafter the produced water was subjected to azeotropicdehydration with stirring at 120° C. for 3 hours to remove 18 g ofwater.

After cooling to 40° C., 79.3 g (1.1 mol) of acrylic acid, 0.12 g ofhydroquinone monomethyl ether and 7.5 g of sulfuric acid were added tothe flask, and the produced water was subjected to azeotropicdehydration with stirring at 120° C. for 3 hours to remove 18 g ofwater.

After cooling, 200 g of a 10% aqueous NaOH solution was added to thereaction mixture, followed by stirring for 30 minutes. Thereafter, thereaction mixture was transferred to a separating funnel, and the aqueousphase was separated and removed, thereby to remove the syntheticcatalyst and excess acrylic acid.

The reaction mixture subjected to washing with alkali and containingtoluene was transferred to the flask, and the solvent was distilled offunder reduced pressure to obtain 205 g of a compound represented by thefollowing formula. This compound had a viscosity of 890 mPas/25° C., butgradually became solid when stored at room temperature (melting point50° C.) The compound was a compound of the formula (2) in which R₈ andR₉ are H, and s=1, and this compound is called A-1. Data ofidentification of A-1 are shown below.

A-1 (white solid, m.p. 50° C., refractive index 1.517, specific gravity1.199)

¹H-NMR (270 MHz, CDCl₃) δ 1.65-1.90(4H, —CH₂—CH ₂—CH ₂—CH₂—, m),2.25-2.45(4H, —CH ₂—CH₂—CH₂—CH ₂—, m), 3.80(2H, —N—CH ₂—, t), 4.30(2H,—CO₂—CH ₂—, t), 5.85(1H, CH ₂═CH—, d), 6.10(1H, CH₂═CH—, dd), 6.40(1H,CH ₂═CH—, d); ¹³C-NMR (67.8 MHz, CDCl₃) δ 19.9, 21.2, 36.3, 61.8, 127.9,131.1, 141.6, 165.7, 170.6; IR(KBr) 2943, 1769, 1708, 1633, 1435, 1399,1369, 1187, 1017, 986, 812 cm⁻¹.

EXAMPLE 2

The reaction and the after-treatment were carried out in the same manneras in Example 1, except that ethanolamine in Example 1 was changed to75.1 g (1.0 mol) of 1-amino-2-propanol, thereby obtaining 220 g of acompound represented by the following formula. Viscosity of the compoundwas 1040 mPas/25° C.

The compound was a compound of the formula (2) in which R₈ was H and R₉was CH₃, and s=1, and this compound is called A-2. Data ofidentification of A-2 are shown below.

A-2 (light yellow liquid, viscosity 1040 mPas/25° C., refractive index1.511, specific gravity 1.171).

¹H-NMR (270 MHz, CDCl₃) δ 1.25(3H, —CH ₃, d), 1.70-1.95(4H, —CH₂—CH ₂—CH₂—CH₂—, m), 2.25-2.45(4H, —CH ₂—CH₂—CH₂—CH ₂—, m), 3.70(2H, —N—CH ₂—,m), 5.15(H, —CO₂—CH—, m), 5.85(1H, CH ₂═CH—, d), 6.10(1H, CH₂═CH—, dd),6.40(1H, CH ₂═CH—, d); ¹³C-NMR (67.8 MHz, CDCl₃) δ17.9, 20.3, 21.6,41.9, 69.3, 128.9, 131.2, 141.9, 165.9, 171.2; IR(neat) 2941, 1767,1710, 1637, 1619, 1429, 1401, 1294, 1270, 1194, 1050, 1028, 911, 810cm⁻¹.

EXAMPLE 3

The reaction and the after-treatment were carried out in the same manneras in Example 1, except that ethanolamine in Example 1 was changed to105.1 g (1.0 mol) of 2-(2-aminoethoxy)ethanol, thereby obtaining 230 gof a compound represented by the following formula. Viscosity of thecompound was 246 mPas/25° C.

The compound was a compound of the formula (2) in which R₈ and R₉ wereH, and s=2, and this compound is called A-3. Data of identification ofA-3 are shown below.

A-3 (light yellow liquid, viscosity 370 mPas/25° C., refractive index1.511, specific gravity 1.190).

¹H-NMR (270 MHz, CDCl₃) δ 1.70-1.95(4H, —CH₂—CH ₂—CH ₂—CH₂—, m),2.25-2.40(4H, —CH ₂—CH₂—CH₂—CH ₂—, m), 3.70(6H, —N—CH ₂, —OCH ₂—CH ₂—O—,m), 4.15(2H, —CO₂—CH ₂—, m), 5.85(1H, CH ₂═CH—, d), 6.15(1H, CH₂═CH—,dd), 6.45(1H, CH ₂═CH—, d); ¹³C-NMR (67.8 MHz, CDCl₃) δ 19.8, 21.2,36.4, 63.5, 68.0, 68.1, 128.1, 130.7, 141.4, 165.8, 170.8; IR(neat)2943, 2865, 1767, 1707, 1636, 1620, 1432, 1401, 1356, 1296, 1271, 1194,1130, 1068, 1018, 987, 811 cm⁻¹.

EXAMPLE 4

The reaction and the after-treatment were carried out in the same manneras in Example 1, except that acrylic acid in Example 1 was changed to86.1 g (1.0 mol) of methacrylic acid, thereby obtaining 210 g of acompound represented by the following formula. Viscosity of the compoundwas 395 mPas/25° C.

The compound was a compound of the formula (2) in which R₈ was CH₃ andR₉ was H, and s=1, and this compound is called M-1. Data ofidentification of M-1 are shown below.

M-1 (light yellow liquid, viscosity 395 mPas/25° C., refractive index1.514, specific gravity 1.175).

¹H-NMR (270 MHz, CDCl₃) δ 1.65-1.85(4H, —CH₂—CH ₂—CH ₂—CH₂—, m),1.95(3H, CH₂═C-CH ₃, s), 2.25-2.45(4H, —CH ₂—CH₂—CH₂—CH ₂—, m), 3.80(2H,—N—CH ₂—, t), 4.30(2H, —CO₂—CH ₂—, t), 5.60(1H, CH ₂═C—, s), 6.10(1H, CH₂═C—, s); ¹³C-NMR (67.8 MHz, CDCl₃) δ 18.0, 19.8, 21.1, 36.3, 62.0,125.9, 135.7, 141.5, 166.8, 170.6; IR(neat) 2944, 1771, 1709, 1637,1431, 1397, 1365, 1319, 1295, 1167, 1017, 993, 944, 816, 739, 716 cm⁻¹.

EXAMPLE 5

The reaction and the after-treatment were carried out in the same manneras in Example 2, except that acrylic acid in Example 2 was changed to86.1 g (1.0 mol) of methacrylic acid, thereby obtaining 220 g of acompound represented by the following formula. Viscosity of the compoundwas 1202 mPas/25° C.

The compound was a compound of the formula (2) in which R₈ and R₉ wereCH₃, and s=1, and this compound is called M-2. Data of identification ofM-2 are shown below.

M-2 (light yellow liquid, viscosity 1202 mPas/25° C., refractive index1.507, specific gravity 1.148).

¹H-NMR (270 MHz, CDCl₃) δ 1.25(3H, —CH₃, d), 1.70-1.90(4H, —CH₂—CH ₂—CH₂—CH₂—, m), 1.95(3H, CH₂═C-CH ₃, s), 2.25-2.45(4H, —CH ₂—CH₂—CH₂—CH ₂—,m), 3.70(2H, —N—CH ₂—, m), 5.15(H, —CO₂—CH—, m), 5.60(1H, CH ₂═C—, s),6.10(1H, CH ₂═C—, s); ¹³C-NMR (67.8 MHz, CDCl₃) δ 17.4, 18.0, 19.8,21.1, 41.4, 68.9, 125.6, 136.1, 141.4, 166.6, 170.6; IR(neat) 2939,1767, 1713, 1637, 1450, 1430, 1400, 1384, 1322, 1292, 1169, 1127, 1029,947, 912, 814, 744, 719 cm⁻¹.

EXAMPLE 6

The reaction and the after-treatment were carried out in the same manneras in Example 3, except that acrylic acid in Example 3 was changed to86.1 g (1.0 mol) of methacrylic acid, thereby obtaining 225 g of acompound represented by the following formula. Viscosity of the compoundwas 246 mPas/25° C.

The compound was a compound of the formula (2) in which R₈ was CH₃ andR₉ was H, and s=2, and this compound is called M-3. Data ofidentification of M-3 are shown below.

M-3 (light yellow liquid, viscosity 246 mPas/25° C., refractive index1.508, specific gravity 1.167).

¹H-NMR (270 MHz, CDCl₃) δ 1.70-1.90(4H, —CH₂—CH ₂—CH ₂—CH₂—, m),1.95(3H, CH₂═C—CH ₃, s), 2.25-2.40(4H, —CH ₂—CH₂—CH₂—CH ₂—, m), 3.65(6H,—N—CH ₂—, —OCH₂—CH ₂—O—, m), 4.15(2H, —CO₂—CH ₂—, m), 5.60(1H, CH ₂═C—,s), 6.10(1H, CH ₂═C—, s);

¹³C-NMR (67.8 MHz, CDCl₃) δ 18.1, 19.8, 21.1, 36.5, 63.6, 67.9, 68.2,125.4, 136.0, 141.3, 167.0, 170.8;

IR(neat) 2943, 2866, 1768, 1709, 1637, 1433, 1398, 1319, 1296, 1169,1128, 1016, 945, 872, 816, 716 cm⁻¹.

EXAMPLE 7

50 Grams of A-1, 47.5 g of propylene glycol monomethyl ether acetate and2.5 g of 2,2′-azobis(2-methylbutyronitrile) were charged in a flakequipped with a stirrer, a thermometer and a condenser tube at roomtemperature, to perform uniform dissolution. Then, the solution washeated and stirred at 85° C. for 2 hours and at 95° C. for 1 hour. Afterthe reaction, substantially no monomer remained.

5 Grams of toluene was added to 10 g of the resulting viscous liquidcontaining a polymer, followed by adding dropwise the liquid little bylittle to 500 ml of methanol strongly stirred in a 1 liter beaker, and asolid precipitated in methanol was filtered off. Then, the solid wassubjected to solvent drying under reduced pressure to obtain 3.2 g of apolymer. This is called P-1. Data of identification of P-1 are shownbelow.

P-1 (white solid) solution viscosity 95 mPas/25° C. (50 wt % toluenesolution), molecular weight (Mn=6500, Mw=32100).

¹H-NMR (270 MHz, CDCl₃) δ 1.40-1.90(6H, br m), 2.10-2.45(5H, br m),3.50-3.80(2H, br m), 3.90-4.40(2H, br m);

¹³C-NMR (67.8 MHz, CDCl₃) δ 19.9, 21.3, 36.1, 36.4, 41.2, 61.7, 141.5,170.6, 174.0;

IR(KBr) 2944, 1739, 1707, 1432, 1398, 1320, 1245, 1159, 1076, 1015, 945,739, 716 cm⁻¹.

EXAMPLE 8

Polymerization was carried out in the same manner as in Example 7,except that 25 g (0.25 mol) of methyl methacrylate (hereinafter referredto as “MMA”) and 25 g (0.10 mol) of A-1 were used in place of 50 g ofA-1 in Example 7. After the reaction, substantially no monomer remained.

Purification was carried out in the same manner as in Example 7 toobtain 3.5 g of a polymer. This is called P-2. Data of identification ofP-2 are shown below. The ratio of A-1 and MMA in the polymer obtained by¹H-NMR was A-1: MMA=2.9:7.1 (molar ratio).

P-2 (white solid), solution viscosity 172 mPas/25° C. (50 wt % toluenesolution), molecular weight (Mn=5600, Mw=16200).

¹H-NMR (270 MHz, CDCl₃) δ 0.80-1.30 (br m), 1.40-2.20 (br m), 2.25-2.45(br m), 3.45-3.85 (br m), 3.95-4.30 (br m);

¹³C-NMR (67.8 MHz, CDCl₃) δ 16.5, 17.8, 20.0, 21.3, 35.9, 44.5, 44.9,51.7, 54.4, 61.8, 141.7, 170.7, 176.8, 177.8;

IR(KBr) 2950, 1734, 1709, 1434, 1399, 1243, 1149, 1078, 991, 945, 748,716 cm⁻¹.

EXAMPLE 9

Polymerization was carried out in the same manner as in Example 8,except that 25 g (0.095 mol) of A-2 was used in place of 25 g of A-1 inExample 8. After the reaction, substantially no monomer remained.

Purification was carried out in the same manner as in Example 7 toobtain 3.5 g of a polymer. This is called P-3. Data of identification ofP-3 are shown below. The ratio of A-2 and MNA in the polymer obtained by¹H-NMR was A-2: MMA 2.8:7.2 (molar ratio).

P-3 (white solid) solution viscosity 451 mPas/25° C. (50 wt % toluenesolution), molecular weight (Mn=8000, Mw=24100).

¹H-NMR (270 MHz, CDCl₃) δ 0.75-1.35 (br m), 1.40-2.20 (br m), 2.25-2.45(br m), 3.40-3.80 (br m), 4.80-5.20 (br m);

¹³C-NMR (67.8 MHz, CDCl₃) δ 16.5, 17.3, 17.5, 18.7, 19.9, 21.3, 41.3,44.5, 44.8, 51.7, 54.3, 68.9, 141.5, 170.6, 177.8, 178.0;

IR(KBr) 2991, 2949, 1733, 1712, 1434, 1402, 1385, 1243, 1149, 1033, 989,912, 746, 717 cm-¹.

EXAMPLE 10

Polymerization was carried out in the same manner as in Example 8,except that 25 g (0.085 mol) of A-3 was used in place of 25 g of A-1 inExample 8. After the reaction, substantially no monomer remained.

Purification was carried out in the same manner as in Example 7 toobtain 3.9 g of a polymer. This is called P-4. Data of identification ofP-4 are shown below. The ratio of A-3 and MMA in the polymer obtained by¹H-NMR was A-3: MMA 2.2:7.8 (molar ratio).

P-4 (white solid) solution viscosity 373 mPas/25° C. (50 wt % toluenesolution), molecular weight (Mn=7500, Mw=24700).

¹H-NMR (270 MHz, CDCl₃) δ 0.80-1.30 (br m), 1.40-2.20 (br m), 2.25-2.45(br m), 3.50-3.85 (br m), 4.00-4.30 (br m);

¹³C-NMR (67.8 MHz, CDCl₃) δ 16.4, 17.7, 18.6, 19.9, 21.2, 36.6, 44.4,44.8, 51.7, 54.2, 63.4, 68.0, 141.5, 170.9, 176.8, 177.7;

IR(KBr) 2951, 1734, 1708, 1435, 1400, 1243, 1148, 1018, 989, 945, 843,750, 716 cm-⁻¹.

EXAMPLE 11

Polymerization was carried out in the same manner as in Example 8,except that 25 g (0.095 mol) of M-1 was used in place of 25 g of A-1 inExample 8. After the reaction, substantially no monomer remained.

Purification was carried out in the same manner as in Example 7 toobtain 4.1 g of a polymer. This is called P-5. Data of identification ofP-5 are shown below. The ratio of M-1 and MMA in the polymer obtained by¹H-NMR was M-1: MMA 2.9:7.1 (molar ratio).

P-5 (white solid) solution viscosity 663 mPas/25° C. (50 wt % toluenesolution), molecular weight (Mn=6300, Mw=17900).

¹H-NMR (270 MHz, CDCl₃) δ 0.70-1.50 (br m), 1.65-2.20 (br m), 2.25-2.45(br m), 3.50-3.90 (br m), 3.95-4.30 (br m);

¹³C-NMR (67.8 MHz, CDCl₃) δ 16.4, 18.6, 19.9, 21.2, 35.7, 44.4, 44.8,45.4, 50.6, 54.3, 62.1, 141.7, 170.5, 176.8, 177.7;

IR(KBr) 2993, 2950, 1732, 1709, 1485, 1434, 1399, 1362, 1271, 1242,1191, 1148, 1076, 993, 945, 748, 716 cm⁻¹.

EXAMPLE 12

Polymerization was carried out in the same manner as in Example 8,except that 25 g (0.195 mol) of butyl acrylate (hereinafter referred toas “BA”) was used in place of 25 g of MMA in Example 8. After thereaction, substantially no monomer remained.

5 Grams of toluene was added to 10 g of the resulting viscous liquidcontaining a polymer, followed by adding dropwise the liquid little bylittle to 500 ml of methanol strongly stirred in a 1 liter beaker, butno solid was precipitated in methanol, and when stirring was stopped, aviscous liquid retained at the bottom of the beaker. The viscous liquidwas subjected to solvent drying under reduced pressure to obtain 1.2 gof a polymer. This is called P-6. Data of identification of P-6 areshown below. The ratio of A-1 and BA in the polymer obtained by ¹H-NMRwas A-1: BA=3.3:6.7 (molar ratio).

P-6 (viscous liquid) solution viscosity 63 mPas/25° C. (50 wt % toluenesolution), molecular weight (Mn=9800, Mw=41900).

¹H-NMR (270 MHz, CDCl₃) δ 0.80-1.05 (br m), 1.20-2.15 (br m), 2.15-2.45(br m), 3.60-3.85 (br m), 3.85-4.40 (br m);

¹³C-NMR (67.8MHz, CDCl₃) δ 13.7, 19.1, 20.0, 21.3, 30.6, 36.2, 36.4,41.4, 61.8, 64.4, 141.6, 170.6, 174.0, 174.4;

IR(KBr) 2959, 2874, 1735, 1710, 1433, 1398, 1248, 1164, 1119, 1063,1016, 945, 739, 721 cm⁻¹.

EXAMPLE 13

Polymerization was carried out in the same manner as in Example 8,except that 25 g (0.240 mol) of styrene (hereinafter referred to as“St”) was used in place of 25 g of MMA in Example 8. After the reaction,substantially no monomer remained.

Purification was carried out in the same manner as in Example 7 toobtain 3.9 g of a polymer. This is called P-7. Data of identification ofP-7 are shown below. The ratio of A-1 and St in the polymer obtained by¹H-NMR was A-1: St=2.9:7.1 (molar ratio).

P-7 (white solid) solution viscosity 92 mPas/25° C. (50 wt % toluenesolution), molecular weight (Mn=6600, Mw=22700).

¹H-NMR (270 MHz, CDCl₃) δ 0.80-2.00 (br m), 2.20-2.45 (br m), 3.30-4.20(br m), 6.40-7.40 (br m);

¹³C-NMR (67.8 MHz, CDCl₃) δ 19.9, 21.2, 36.1, 40.8, 60.9, 125.2, 125.9,128.0, 128.1, 129.0, 141.5, 170.5, 175.2;

IR(KBr) 3026, 2934, 1735, 1709, 1494, 1452, 1432, 1397, 1370, 1244,1152, 1113, 1074, 1017, 945, 762, 701 cm⁻¹.

EXAMPLE 14

Polymerization was carried out in the same manner as in Example 8,except that 25 g of A-1 was changed to 45 g (0.181 mol), 5 g (0.039 mol)of BA was used in place of MMA, propylene glycol monomethyl etheracetate was changed to 49 g, and 2,2′-azobis(2-methylbutyronitrile) waschanged to 1.0 g. After the reaction, substantially no monomer remained.

Purification was carried out in the same manner as in Example 7 toobtain 2.0 g of a polymer. This is called P-8. Data of identification ofP-8 are shown below. The ratio of A-1 and BA in the polymer obtained by¹H-NMR was A-1: BA=8.2:1.8 (molar ratio).

Solution viscosity 138 mPas/25° C. (50 wt % toluene solution), molecularweight (Mn=8200, Mw=33800).

¹H-NMR (270 MHz, CDCl₃) δ 0.85-1.05 (br m), 1.20-2.10 (br m), 2.10-2.55(br m), 3.60-3.85 (br m), 3.85-4.40 (br m);

¹³C-NMR (67.8 MHz, CDCl₃) δ 13.7, 19.0, 20.0, 21.2, 30.5, 36.1, 36.4,41.2, 61.7, 64.3, 141.5, 170.6, 174.0;

IR(KBr) 2943, 2864, 1738, 1706, 1432, 1398, 1321, 1244, 1160, 1114,1077, 1015, 944, 876, 824, 739, 715 cm⁻¹.

EXAMPLE 15

Polymerization was carried out in the same manner as in Example 8,except that 20 g (0.076 mol) of M-1 was used in place of 25 g of A-1,the weight of MMA was changed to 30 g (0.300 mol), propylene glycolmonomethyl ether acetate was changed to 50 g, and2,2′-azobis(2-methylbutyronitrile) was changed to 0.25 g. After thereaction, substantially no monomer remained.

5 Grams of toluene was added to 10 g of the resulting viscous liquidcontaining a polymer, followed by adding dropwise the liquid little bylittle to 500 ml of methanol strongly stirred in a 1 liter beaker, butno solid was precipitated in methanol, and when stirring was stopped, aviscous liquid retained at the bottom of the beaker. The viscous liquidwas subjected to solvent drying under reduced pressure to obtain 3.0 gof a polymer. This is called P-9. Data of identification of P-9 areshown below. The ratio of M-1 and MMA in the polymer obtained by ¹H-NMRwas M-1: MMA=2.0:8.0 (molar ratio).

Solution viscosity 644 mPas/25° C. (50 wt % toluene solution), molecularweight (Mn=26200, Mw=70800).

¹H-NMR (270 MHz, CDCl₃) δ 0.70-1.50 (br m), 1.65-2.15 (br m), 2.25-2.60(br m), 3.50-3.70 (br m), 3.70-3.90 (br m), 3.95-4.20 (br m);

¹³C-NMR (67.8 MHz, CDCl₃) δ 16.3, 18.6, 19.9, 21.2, 35.6, 44.4, 44.8,51.7, 52.5, 54.3, 62.1, 141.6, 170.7, 176.9, 177.8, 178.1;

IR(KBr) 2994, 2949, 1734, 1709, 1485, 1434, 1399, 1362, 1271, 1243,1192, 1147, 1076, 993, 966, 945, 843, 748, 716 cm⁻¹.

EXAMPLE 16

70 Parts of acrylate A-1 obtained in Example 1 and 30 parts of a mixtureof pentaacrylate of dipentaerythritol (about 20% by weight) andhexaacrylate of dipentaerythritol (about 80% by weight) (Aronix M-400manufactured by Toagosei Co., Ltd.) were mixed by conventional method toobtain a radiation-curable composition.

The resulting composition was evaluated on curability, weatherresistance, abrasion resistance and adhesiveness by the followingmethods. The results are shown in Table 2.

Curability:

The resulting composition was coated at a thickness of 10μ on aBonderite steel sheet (PB-144 manufactured by Japan Test Panel Co.,Ltd.) as a substrate, and this was passed under a 120 W/cm condensingtype high pressure mercury lamp (one lamp) at a conveyor speed of 5m/min. The curability was evaluated in terms of the number of passingbefore the surface became tack-free.

Weather resistance:

The resulting composition was coated at a thickness of 10μ on a whitePVC sheet manufactured by Japan Test Panel Co., Ltd. as a substrate, andthis was passed under a 120 W/cm condensing type high pressure mercurylamp (one lamp, height: 10 cm)) at a conveyor speed of 5 m/min. Thecomposition cured until the surface became tack-free was employed as atest specimen.

The test specimen was exposed to wetting conditions (100%RH/40° C.) for6 hours and irradiation conditions (30 W/m²/40° C.) for 6 hoursalternately for 500 hours using a dew panel light control weatherometerDPWL-5R manufactured by Suga Tester Co., Ltd. as an accelerated exposuretester. Change in appearance was visually examined, and discolorationwas evaluated by a differential calorimeter Sigma 80 manufactured byNihon Denshoku Co., Ltd. In Table 2, the symbols “∘”, “Δ”, and “X” inthe change of appearance have the following meanings.

“∘”: No cracks occurred.

“Δ”: Some cracks occurred.

“X”: Cracks occurred on the whole of the coat.

Abrasion resistance:

The resulting composition was coated at a thickness of 10μ on apolycarbonate sheet manufactured by Japan Test Panel Co., Ltd. as asubstrate, and this was passed under a 120 W/cm condensing type highpressure mercury lamp (one lamp, height: 10 cm)) at a conveyor speed of5 m/min. The composition cured until the surface became tack-free wasemployed as a test specimen.

A steel wool of #000 was attached to a tip of a cylinder of 25 mm indiameter, and allowed to contact with the cured coat of the testspecimen placed horizontally and rotated five times (20 rpm) under aload of 1.0 kg. Degree of flawing was visually examined. In Table 2, thesymbols “⊚”, “∘”, “Δ”, and “X” have the following meanings.

“⊚”: No flaws were caused on the surface of the specimen.

“∘”: Some flaws were caused on the surface of the specimen.

“Δ”: Considerable flaws were caused on the surface of the specimen.

“X”: The surface of the substrate at the flaw portions was exposed.

Adhesiveness:

The same test specimen as used in the abrasion resistance test wassubjected to the cellophane tape peeling test in accordance with JISK-5400. The adhesion was evaluated in terms of the number of theremaining squares per 100 squares according to the following criteria.The substrate was a polycarbonate sheet manufactured by Japan Test PanelCo., Ltd.

“∘”: More than 90 squares.

“Δ”: 10-90 squares.

“X”: Less than 10 squares.

Odor:

The cured coat of the composition was smelled just after curing, andevaluation was conducted by the following criteria.

“∘”: Substantially no odor.

“Δ”: Slight odor.

“X”: Considerable odor.

“XX”: Strong odor.

EXAMPLES 17-21

Radiation-curable compositions were prepared in the same manner as inExample 16 using A-1 to A-3 obtained in Examples 1-3, except for usingthe ingredients and the formulations as shown in Table 1.

The resulting compositions were evaluated in the same manner as inExample 16. The results are shown in Table 2.

TABLE 1 Irg Tinuvin Tinuvin Example A-1 A-2 A-3 M-400¹⁾ M-1600²⁾M-8060³⁾ M-309⁴⁾ 184⁵⁾ 144⁶⁾ 328⁷⁾ 16 70 — — 30 — — — — — — 17 — 30 — 60— — 10 0.5 — — 18 — — 80 — 20 — — — — — 19 40 — — 30 — 30 — — 0.2 0.2 2020 — — 60 20 — — — 0.5 0.5 21 — 30 — — 30 — 40 — 0.5 0.5 ¹⁾M-400: AronixM-400 manufactured by Toagosei Co., Ltd., a mixture of pentaacrylate ofdipentaerythritol (about 20% by weight) and hexaacrylate ofdipentaerythritol (about 80% by weight). ²⁾M-1600: Aronix M-1600manufactured by Toagosei Co., Ltd., non-yellowing urethane diacrylate.³⁾M-8060: Aronix M-8060 manufactured by Toagosei Co., Ltd., polyesterpolyacrylate. ⁴⁾M-309: Aronix M-309 manufactured by Toagosei Co., Ltd.,trimethylolpropane triacrylate. ⁵⁾Irg 184: Irgacure 184 manufactured byCiba-Geigy Corp., hydroxycyclohexylacetophenone (photopolymerizationinitiator). ⁶⁾Tinuvin 144: Tinuvin 144[bis(1,2,2,6,6-pentamethyl-4-piperidyl2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate)] (lightstabilizer) manufactured by Ciba-Geigy Corp. ⁷⁾Tinuvin 328: Tinuvin 328[2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole] (ultraviolet absorber)manufactured by Ciba-Geigy Corp.

TABLE 2 Weather resistance Curability ΔE (Number Color of Appear-differ- Abrasion Adhesive- Example passing) ance ence resistance nessOdor 16 3 ∘ 1.0 ∘ ∘ ∘ 17 2 ∘ 1.5 ⊚ ∘ Δ 18 3 ∘ 0.8 ∘ ∘ ∘ 19 2 ∘ 1.1 ⊚ ∘ ∘20 3 ∘ 0.8 ⊚ ∘ ∘ 21 4 ∘ 0.5 ⊚ ∘ ∘

EXAMPLES 22-24

Radiation-curable compositions were prepared in the same manner as inExample 16 using M-1 to M-3 obtained in Examples 4-6, except for usingthe additives and the formulations as shown in Table 3.

The resulting compositions were evaluated in the same manner as inExample 16 on curability, abrasion resistance, adhesion and odor. Theresults are shown in Table 3. These compositions had the weatherresistance similar to that of Examples 16-21.

TABLE 3 Curability (Number Abrasion of resist- Adhesive- Example M-1 M-2M-3 M-400 M-8060 passing) ance ness Odor 22 50 — — 50 — 2 ◯ ◯ ◯ 23 — 70— 30 — 2 ◯ ◯ ◯ 24 — — 30 — 70 3 ◯ ◯ ◯

COMPARATIVE EXAMPLES 1-3

Radiation-curable compositions were prepared in the same manner as inExample 16, except for using the additives and the formulations as shownin Table 4.

The resulting compositions were evaluated in the same manner as inExample 16. The results are shown in Table 5.

TABLE 4 Compara- Vis- tive coat Irg Benzo- Tinuvin Tinuvin ExampleM-120⁸⁾ #190⁹⁾ M-400 M-1600 M-8060 M-309 184 phenone 144 328 1 80 — — 20— — 1 1 — — 2 40 — 30 — 30 — 2 — 0.5 0.5 3 — 30 — 30 — 40 2 — 0.5 0.5⁸⁾M-120: Aronix M-120 manufactured by Toagosei Co., Ltd., 2-ethylhexylacrylate modified with 2 mols of ethylene oxide. ⁹⁾Viscoat #190:Ethoxyethoxyethyl acrylate manufactured by Osaka Yuki Kagaku Co., Ltd.

TABLE 4 Compara- Vis- tive coat Irg Benzo- Tinuvin Tinuvin ExampleM-120⁸⁾ #190⁹⁾ M-400 M-1600 M-8060 M-309 184 phenone 144 328 1 80 — — 20— — 1 1 — — 2 40 — 30 — 30 — 2 — 0.5 0.5 3 — 30 — 30 — 40 2 — 0.5 0.5⁸⁾M-120: Aronix M-120 manufactured by Toagosei Co., Ltd., 2-ethylhexylacrylate modified with 2 mols of ethylene oxide. ⁹⁾Viscoat #190:Ethoxyethoxyethyl acrylate manufactured by Osaka Yuki Kagaku Co., Ltd.

EXAMPLES 25-32

One gram of P-1 was added to 9 g of Aronix M-305 manufactured byToagosei Co., Ltd. (pentaerythritol triacrylate), followed by stirringat 80° C. to dissolve P-1 to obtain a radiation-curable composition(Example 25).

Furthermore, radiation-curable compositions were prepared in the samemanner as in Example 25, except for changing the formulations to thoseshown in Table 6 (Examples 26-32).

The resulting compositions were evaluated on curability, solventresistance, pencil hardness and odor by the following methods. Theresults are shown in Table 7. These compositions had the weatherresistance similar to that of Examples 16-21.

Curability:

The composition was coated on a phosphoric acid-treated iron sheet(PB144 manufactured by Japan Test Panel Co., Ltd.) by bar coater #10,and cured by irradiation with ultraviolet rays under the same conditionsas in Example 16, except that the lamp output was changed from 120 W/cmto 80 W/cm, and the conveyor speed was changed from 5 m/min to 10 m/min.The curability was evaluated in terms of the number of passing as inExample 16.

Solvent resistance:

The cured coat was rubbed with a swab impregnated with acetone, and thesolvent resistance was evaluated in terms of the number of rubbingbefore the coat was whitened or broken.

Pencil hardness:

This was measured in accordance with JIS K-5400.

Odor:

The cured coat of the composition was smelled just after curing, andevaluation was conducted by the following criteria.

“∘”: Substantially no odor.

“Δ”: Slight odor.

“X”: Considerable odor.

“XX”: Strong odor.

TABLE 6 Example P-1 P-2 P-3 P-4 P-5 P-6 P-7 P-8 P-9 M-305 M-210 25 10 —— — — — — — — 90 — 26 10 — — — — — — — — — 90 27 — 10 — — — — — — — 90 —28 — — 10 — — — — — — 90 — 29 — — — 10 — — — — — 90 — 30 — — — — 10 — —— — 90 — 31 — — — — — 10 — — — 90 — 32 — — — — — — 10 — — 90 — 33 — — —— — — — 10 — 90 — 34 — — — — — — — — 10 90 —

TABLE 7 Curability (Number of Solvent Pencil Example passing) resistancehardness Odor 25 4 >50 3H ∘ 26 2 >50 3H ∘ 27 5 >50 2H ∘ 28 6 >50 2H ∘ 296 >50 2H ∘ 30 6 >50 3H ∘ 31 8 >50 2H ∘ 32 7 >50 2H ∘ 33 5 >50 3H ∘ 345 >50 3H ∘

COMPARATIVE EXAMPLE 4

Radiation-curable compositions were prepared in the same manner as inExample 16, except for using the additives and the formulations as shownin Table 8.

The resulting compositions were evaluated in the same manner as inExample 25. The results are shown in Table 8.

TABLE 8 Curabil- ity (Num- Pencil Comparative Irg ber of Solvent Hard-Example M-305 651¹⁰⁾ passing) resistance ness Odor 4 100 1 3 >50 3H x¹⁰⁾Irg 651:Irgacure 651, benzildimethyl ketal, manufactured by CibaSpecialty Chemicals Co., Ltd.

INDUSTRIAL APPLICABILITY

The imido (meth)acrylate of the present invention can be easilyproduced, is readily cured by irradiation with radiations, and,furthermore, has excellent curability without photopolymerizationinitiator even when it is cured by irradiation with ultraviolet rays.Moreover, cured products have substantially no odor and have excellentweather resistance, abrasion resistance and adhesiveness.

The radiation-curable compositions containing the imido (meth)acrylateof the present invention or a polymer containing the imido(meth)acrylate as a constitutive monomer have the above-mentionedproperties and can be utilized as coating agents, adhesives and moldingmaterials with excellent properties, and can be utilized in paint,adhesive and plastic molding techniques.

What is claimed is:
 1. A radiation-curable composition which contains animido (meth)acrylate represented by the following formula, and a(meth)acrylate having 2 or more (meth)acryloyl groups in one molecule:

wherein R₁, R₂ and R₃ each represents H or CH₃, and R₁, R₂ and R₃ in onemolecule may be the same or different, R₄-R₇ each represent H orCH_(m)H_(2m+1)(m=1-6), and R₄-R₇ in one molecule may be the same ordifferent, and n=1-4.
 2. A radiation-curable composition according toclaim 1, wherein the constitutional ratio of the imido (meth)acrylateand the (meth)acrylate is 5-95% by weight: 95-5% by weight.
 3. Aradiation-curable composition according to claim 1, wherein R₃-R₇ of theimido (meth)acrylate each represents H.
 4. An ultravioletradiation-curable composition which contains an imido (meth)acrylaterepresented by the following formula:

wherein R₁, R₂ and R₃ each represents H or CH₃, and R₁, R₂ and R₃ in onemolecule may be the same or different, R₄-R₇ each represents H orC_(m)H_(2m+1)(m=1-6), and R₄-R₇ in one molecule may be the same ordifferent, and n=1-4; and a (meth)acrylate having 2 or more(meth)acryloyl groups in one molecule, and substantially free of a photoinitiator.
 5. An ultraviolet radiation-curable composition according toclaim 3, wherein R₃-R₇ of the imido (meth)acrylate each represents H. 6.An ultraviolet radiation-curable composition according to claim 3,wherein the constitutional ratio of the imido (meth)acrylate, and the(meth)acrylate is 5-95% by weight: 95-5% by weight.